Sigwok to society of chemical indttstby in basle



Patented June 7, 1927.

UNITED STATES PAT SWIG-EL IPOSTERNAK, 0F

SIGNOR TO SOCIETY OF CHEM LAND.

rnosriaonus com.

ICALLY No Drawing. Application filed January 11, 1924, Serial No. 685,?1T,

ENT OFFICE.

In specification (Serial No. 652,851 of July 20th, 1923,) there is described a process in which by digesting commercial casein with trypsin casein, however,

amount of mineral pho preparation of the chemical pound a matter of great difiiculty.

almost the. whole phosphorus content thereof may be separated in form-of a soluble calcium salt.

contains a The commercia considerable sphates, rendering the ly pure com- On the one hand most substances which precipitate the former also precipitate the latter, and

organic compound.

It has now been metal carbonates possess found that the alkali the property of decomposing theheavy metal salts of the phosphorus containing even in the cold conver alkali metal salts,

meanwhile remaining compounds in question ting theminto soluble the metallic phosphates undissolved. The

mineral phosphoric acid may be separated quantitatively by means 0 very simple manner.

By the present invention horns-containing nuclear from the organic compound alkali. metal carbonates 1n a the organic phos casein'may be obtained in a chemically pure form by digesting methods in a weakly pancreatic ferments,

the casein by known alkaline solution with precipitating from the filtered digestion liquid by means of a heavy metal salt the heavy metal salt of the organic phosphorus compound, hosphate,

heavy metal p together with the treating the .precipi:

tate so obtained with a solution ofan alkali metal carbonate salt of the organic the alkali metal salt,

from the insoluble mineral cipitating from the solution so obtained byadthe alkali-metal salt of the dition of alcohol,

to convert the heavy metal phosphorus compound into separating the latter phosphate, prechemically pure organic phosphorus compound, dissolving the precipitate so obtained in water, precipitating treatment with a suitheavymetal salt by able salt of a heavy heavy metal from the of hydrogen sulphide, lic sulphide, precipitat the corresponding metal, removing the precipitate by means filtering off the metaling the free-acid from CHENE-BOUGERIES,

IGAL INDUST Y IN BASLE, 0F BASEL. SWITZER- 1 salt with 3 cent of phosphorus.

substance of milk NEAR GENEVA, SWITZERLAND, A8-

AINING. NUCLEAR SUBSTANCE OF MILK GASEIN IN .5. CH- PURE FORM AND PROCESS OF MAKING THE SAME.

and in Switzerland January 25, 1928.

the filtrate by addition of alcohol, and finally drying the precipitated product.

If required the solution of the alkali metal salt of the organic phosphorus compound obtained by decomposition of the heavy metal an alkali metal carbonate may conveniently be subjected before further purification to a second digestion of a short duration with pancreatic ferments, whereupon the digestion liqpid thus obtained, after having been filtere is mixed with alcohol and the alkali metal salt-of, the organic phosphorus compound thus precipitated treated further as described in the preceding parar p he free acid thus obtained is a white amorphous powder which contains 5.86 per It is soluble in water to a clear solution, but is nearly insoluble in alcohol and insoluble in other organic solvents. The aqueous solution reacts neutrally to red Congo paper and is aci to methyl orange and litmus. The aqueous sdlution of the acid does not become turbid on the addition of magnesia mixture, that is to' say, amixture of ammonium chloride, ammonia, and-magnesium precipitateis produced, but no precipitate is Copper obtained with a dilute solution. acetate yields a clear blue precipitate, lead acetate and mercury salts a white precipitate,

silver nitrate and ferric chloride give no precipitate with a solution of the free acid, but

if the solution of the acid be first neutralized with caustic soda solution silver nitrate gives a white precipitate and iron salts a yellow precipitate. The new compound gives the biuret reaction, but does not react to Millons, the xantho-proteic and Molischs test. The alkali salts and the alkaline earth salt-s thereof are soluble in water, but the saturated iron salt and the heavy metal salts .do not dissolve in vwater. The compound is fairly stable towards mineral acids in the cold also towards ammonia and sodium bicarbonateat a temperature below 40 C. By treatment with caustic alkali or barium hydroxide, at ordinary temperature, half of the phosphoric acid is gradually split off, but at the boiling point all the phosphoric acid most spontaneously.

The invention is illustrated by the following example.

v kilos of commercial milk casein are suspended in 80 litres of water previously warmedto40 C; To this suspension there are added 620 grams of anhydrous sodium carbonate, GOO-grams of sodium bicarbonate, 500 grams of finely subdivided pancreas, or and 200 cc. of toluene. e mixture is left to stand first for two days at 40 0., with continuous stirring, and then for another 24 hours in the cold. After tering sugar of lead and an aqueous solution of basic lead acetate are added to the solution until no further precipitate is formed. The lead precipitate, which contains all the phosphorous compounds originally present in the solution, is filtered, thoroughly washed with water, and pressed.

In order to remove the lead from the organic phosphorus compounds and to separate them from the lead phosphate, the lead the . to th acetate or a mercury salt instead of sugar tated by means of hy precipitate is .finely triturated with some water, a sodium carbonate solution of 20 per cent strength being added, while stirring, until the liquid is slightly alkaline to phenolphthaleim Generally about 2 litres of the sodium carbonate solution are necessary. The solution thus formed is then sharply separated from the undissolved lead carbonate and lead phosphate and may conand is left to settle. layer is siphoned ofi water, "and precipitated sugar'of lead. The lead salt is washed and the lead precipirogen sulphide. After filtering off the lead sulphide the acid solutlon is then freed from hydrogen sulphide y an air current, concentrated Ina vacuum at low temperature, and precipitated with 4 volumes of strong alcohol. Finally" the snow-white precipitate so obtained is filtered, washed with alcoliol, dried in a' vacuum at low temperature, and pulverized. It forms e pure phosphorus containing nucleus of he casein. a I It may be remarked that, without altering resu t in any way, the precipitant added e solution of the oil may be copper e upper alcoholic the oil is dissolved in by means of then filtered,

of lead. 7 Further, ammonium carbonate or potassium carbonate may be employed in the place of sodium carbonate.

By neutralization of the free acid withalkahes or alkaline earths and subsequent with of the sodium salt the aforesaid oil may be directly dried in a vacuum. By acting on the sodium salt with a soluble iron salt the iron salt of the organic phosphorus compound is produced.

What I claim is 1. Process for the manufacture of the phosphorus containing organic nuclear substance of milk casein in a chemically pure form, consisting in digesting milk casein, according to known methods, in weakly alkaline solution with pancreatic ferments, filtering the digestiolrliquid and precipitating the filtrate with a salt of a heavy metal, treating the precipitate of the heavy metal salt with an alkali metal carbonate ,SOlLltlOIl, thereby eliminating the heavy metal from the organic phosphorus compound and separating this latter from mineral phosphates, filtering and adding alcohol to the filtrate, dissolving in water the alkali metal salt of the chemically pure phosphorus compound thus precipitated,adding a heavy metal salt to the solution. removing the heavy metalfrom the precipitatethus formed with a compound the kation of which is hydrogen and the anion of which yields with the heavy metal an insoluble salt, separating the latter, precipitating the solution of thus obtained with alcohol, and finally dry-' the free acid ing the duced.

2. Process for the manufacture of the phosphorus containing organic nuclear substance of milk casein in a chemically pure form, consisting in digesting milk casein, according to known methods, in weakly alkaline solution with pancreatic ferments, filtering the digestion liquid and precipitating the filtrate with a salt of a heavy metal, treating the precipitate of the heavy meal salt with an alkali metal carbonate solution, thereby eliminating the heavy metal from the organic phosphorus compound and separating this latter from mineral phosphates, subjecting the solution ob tained by decomposition of the heavy metal of the organic phosphorus compound with alkali metal carbonate to a second digestion pancreatic ferments for a short time, filtering the digestion liquid thus obtained and adding alcohol to the filtrate, dissolving in water the alkali metal salt of the chemically pure phosphorus compound thus precipitated, add the solution, the precipitate thus formed with a compound the kation of which is hydrogen and the anion of which yields with the heavy metal an insoluble salt, separatin the latter, precipitating the solution of tile" free acid thus phosphorus compound thus' promg a heavy metal salt to removing the heavy metal from,

Hit)

stance of milk casein in obtained with alcohol, and finally drying'the phosphorus compound thus produced.

3. Process for the manufacture of the phosphorus containing organic nuclear substance of milk casein in a chemically pure form, consisting in digesting milk casein, according to known methods, in weakly alkaline solution with pancreatic ferments, filtering the digestion liquid and precipitating the filtrate with a salt of a heavy metal, treating the precipitate of the heavy metal salt with an alkali metal carbon ate solutiomtherehy eliminating the heavy metal from the organic phospl'iorus compound and separating this latter from mineral phosphates, filtering and adding alcohol to the filtrate, dissolving in water the alkali metal salt of the chemically pure phosphorus compound thus precipitated, adding a heavy metal salt to the solution, removing the heavy metal from the precipitate thus formed with hydrogen sulfide, separating the insoluble sulfide of the heavy metal thus formed, precipitating the solution of the free acid thus obtained with alcohol, and finally drying the phosphorus compound thus produced.

4. Process for the manufacture of the phosphorus containing organic nuclear suba chemically pure form, consisting in digesting milk casein, according to known methods, in weakly alkaline solution with pancreatic ferments, filtering the ing the filtrate with a salt of a heavy metal,

treating the precipitate of the heavy metal salt with an alkali metal carbonate solution,

thereby eliminating the heavy metal from the organic phosphorus compound and sepadigestion liquid and precipitat pure phosphorus compound thus precipitated, adding :1

tion, removing precipitate thus heavy metal salt to the soluthe heavy metal from the formed with hydrogen sullatter from mineral phosphates, 4

fide, separating the insoluble sulfide of the heavy metal thus formed, precipitating the solution of the free acid thus obtained with alcohol, and finally drying the phosphorus compound thus produced.

5. In the process for the manufacture of the phosphorus containing organic nuclear substance of milk casein in a chemically pure form, the step of decomposing aheavy metal salt of the organic phosphorus compound obtained by the tryptic'digestion of milk ea'scin with a solution of alkali metal carbonate.

6. As a new product the phosphorus con-' taining organic nearly in- I nuclear substance of milk casein, which constitutes in form of the free 

